JPH11322419A - Piezoelectric porcelain composition and its production - Google Patents
Piezoelectric porcelain composition and its productionInfo
- Publication number
- JPH11322419A JPH11322419A JP10136386A JP13638698A JPH11322419A JP H11322419 A JPH11322419 A JP H11322419A JP 10136386 A JP10136386 A JP 10136386A JP 13638698 A JP13638698 A JP 13638698A JP H11322419 A JPH11322419 A JP H11322419A
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- Japan
- Prior art keywords
- sintered body
- heat treatment
- temperature
- polarization
- resonance frequency
- Prior art date
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- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特に厚みすべりモ
ード共振を利用したフィルタに用いるもので電気機械結
合係数が比較的大きく、耐熱性および耐湿性が良好で温
度サイクル前後での共振周波数変化が少ない圧電磁器組
成物およびその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is particularly used for a filter utilizing thickness-shear mode resonance, and has a relatively large electromechanical coupling coefficient, good heat resistance and moisture resistance, and a change in resonance frequency before and after a temperature cycle. The present invention relates to a small piezoelectric ceramic composition and a method for producing the same.
【０００２】[0002]
【従来の技術】従来より圧電磁器組成物としてはチタン
酸ジルコン酸鉛磁器、マグネシウムニオブ酸チタン酸ジ
ルコン酸鉛磁器、および亜鉛ニオブ酸チタン酸ジルコン
酸鉛磁器などがあり、使用目的に応じて種々の改良がな
されてきた。2. Description of the Related Art Conventionally, piezoelectric ceramic compositions include lead zirconate porcelain titanate, lead zirconate porcelain magnesium niobate, and lead zirconate zinc niobate porcelain. Has been improved.
【０００３】[0003]
【発明が解決しようとする課題】フィルタに用いる圧電
磁器組成物は、表面実装タイプのチップ部品に対応する
ため、半田付け実装温度に耐えうる耐熱性と電子機器の
過酷な環境下での使用を前提とした信頼性（特に耐湿
性）が要求されている。The piezoelectric ceramic composition used for the filter is compatible with surface-mount type chip components, so that it has heat resistance enough to withstand the soldering mounting temperature and uses under severe environments of electronic devices. Prerequisite reliability (especially moisture resistance) is required.
【０００４】さらに従来の圧電磁器組成物は実用上に重
要な信頼性の一つである温度サイクル前後で共振周波数
が変化するという問題があり、電子機器の安定動作のた
め共振周波数の変化をできるだけ低く押さえる必要があ
った。Further, the conventional piezoelectric ceramic composition has a problem that the resonance frequency changes before and after a temperature cycle, which is one of reliability which is important for practical use. I needed to keep it low.
【０００５】そこで本発明は、厚みすべりモード共振を
利用したフィルタに適した電気機械結合係数が比較的大
きく、２８０℃近傍の半田付け実装温度でも電気特性劣
化が少なく、高湿度雰囲気下でも電気特性劣化が少な
く、かつ温度サイクルによる共振周波数変化の少ない圧
電磁器組成物を提供することを目的とするものである。Accordingly, the present invention has a relatively large electromechanical coupling coefficient suitable for a filter utilizing thickness-shear mode resonance, and has a small deterioration in electric characteristics even at a soldering mounting temperature near 280 ° C. It is an object of the present invention to provide a piezoelectric ceramic composition which is less deteriorated and has less change in resonance frequency due to a temperature cycle.
【０００６】[0006]
【課題を解決するための手段】この目的を達成するため
に本発明の圧電磁器組成物は、一般式（化３）で表され
る主成分に、副成分としてＣｒ2Ｏ3およびＭｎ3Ｏ4のう
ち少なくとも一種を前記主成分１００重量％に対して
０．０５〜０．８重量％添加して形成したものである。In order to achieve this object, the piezoelectric ceramic composition of the present invention comprises a main component represented by the general formula (Chemical Formula 3) and Cr 2 O 3 and Mn 3 O as subcomponents. 4 is formed by adding at least one of 0.05 to 0.8% by weight to 100% by weight of the main component.
【０００７】[0007]
【化３】 Embedded image
【０００８】この構成によると比較的大きな比誘電率ε
11 T／ε0と電気機械結合係数ｋ15を実現すると同時に良
好な耐熱性、耐湿性と、温度サイクルによる共振周波数
変化を低減できる。According to this configuration, a relatively large relative dielectric constant ε
While realizing 11 T / ε 0 and the electromechanical coupling coefficient k 15 , good heat resistance and moisture resistance and a change in resonance frequency due to a temperature cycle can be reduced.
【０００９】またＰｂ量を化学量論比より若干多くする
ことにより焼成時のＰｂＯ飛散の影響を低減すると同時
に焼結性を高め、Ｐｂの部分Ｌａ置換で耐湿性改善およ
び温度サイクルによる共振周波数変化を低減し、副成分
としてのＣｒ2Ｏ3およびＭｎ 3Ｏ4のうち少なくとも一種
の添加で電圧性を低下させることなく耐熱性を改善し
た。またＰｂの部分Ｌａ置換で比誘電率ε11 T／ε0が上
昇し、フィルターで帯域幅を広くとれるという利点があ
る。Further, the amount of Pb is made slightly larger than the stoichiometric ratio.
This reduces the effect of PbO scattering during firing and
Sinterability is improved, and partial La substitution of Pb improves moisture resistance.
Changes in resonance frequency due to temperature and temperature cycles,
Cr asTwoOThreeAnd Mn ThreeOFourAt least one of
Improves heat resistance without lowering voltage
Was. In addition, the relative permittivity ε11 T/ Ε0Is on
The advantage is that the bandwidth can be widened by the filter.
You.
【００１０】その結果上記目的を達成することができる
のである。As a result, the above object can be achieved.
【００１１】[0011]
【発明の実施の形態】本発明の請求項１に記載の発明
は、一般式（化４）で表される主成分に、副成分として
Ｃｒ2Ｏ3およびＭｎ3Ｏ4の少なくとも一種を前記主成分
１００重量％に対して０．０５〜０．８重量％添加して
形成した圧電磁器組成物であり、厚みすべりモード共振
を利用したフィルタに適した電気機械結合係数が比較的
大きく、２８０℃近傍の半田付け実装温度でも電気特性
劣化の少ない、耐湿性に優れ、温度サイクルによる共振
周波数変化の少ないものである。BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention is characterized in that at least one of Cr 2 O 3 and Mn 3 O 4 is added as a sub-component to the main component represented by the general formula (Formula 4). A piezoelectric ceramic composition formed by adding 0.05 to 0.8% by weight with respect to 100% by weight of a main component, and has a relatively large electromechanical coupling coefficient suitable for a filter utilizing thickness-shear mode resonance, and Even at a soldering mounting temperature of around ℃, there is little deterioration in electrical characteristics, excellent moisture resistance, and little change in resonance frequency due to temperature cycling.
【００１２】[0012]
【化４】 Embedded image
【００１３】請求項２に記載の発明は、一般式（化５）
で表される主成分に、副成分としてＣｒ2Ｏ3およびＭｎ
3Ｏ4の少なくとも一種を前記主成分１００重量％に対し
て０．０５〜０．８重量％添加、混合する第１の工程
と、次にこの混合物を成形して焼成し、焼結体を得る第
２の工程と、次いでこの焼結体表面に分極用電極を形成
し、１３０〜１８０℃の温度範囲において３．０ｋＶ／
ｍｍ以上の直流電界を印加して分極する第３の工程と、
その後この分極済み焼結体の分極用電極間を短絡して、
１５０〜２５０℃の温度下で熱処理温度（℃）と熱処理
時間（時間）の積が１８００以上となる条件下で熱処理
する第４の工程とを備えたことを特徴とする圧電磁器組
成物の製造方法であり、厚みすべりモード共振を利用し
た広帯域のフィルタに適した電気機械結合係数が比較的
大きく、２８０℃近傍の半田付け実装温度でも電気特性
劣化の少ない、耐湿性に優れ、温度サイクルによる共振
周波数変化の少ない圧電磁器組成物を得ることができ
る。The invention according to claim 2 is a compound of the general formula (5)
And Cr 2 O 3 and Mn as accessory components
A first step of adding and mixing at least one type of 3 O 4 in an amount of 0.05 to 0.8% by weight based on 100% by weight of the main component, and then molding and firing the mixture to obtain a sintered body; A second step of obtaining the electrode, and then forming a polarization electrode on the surface of the sintered body, and setting the polarization electrode to 3.0 kV /
a third step of applying a DC electric field of at least
Then short-circuit the electrodes for polarization of this polarized sintered body,
Producing a piezoelectric ceramic composition, comprising: a fourth step of performing heat treatment at a temperature of 150 to 250 ° C. under a condition that a product of a heat treatment temperature (° C.) and a heat treatment time (hour) is 1800 or more. This method has a relatively large electromechanical coupling coefficient suitable for a broadband filter using thickness-shear mode resonance, and has little deterioration in electrical characteristics even at a soldering mounting temperature near 280 ° C, has excellent moisture resistance, and has resonance due to temperature cycling. A piezoelectric ceramic composition with a small frequency change can be obtained.
【００１４】[0014]
【化５】 Embedded image
【００１５】以下本発明の一実施の形態について図面を
参照しながら説明する。 （実施の形態）図１は本実施の形態における厚みすべり
モード共振子の斜視図であり、圧電磁器１の上、下両面
に共振電極２を形成したものである。また図２（ａ），
（ｂ），（ｃ）は、焦電効果による分極済み圧電磁器熱
処理時の脱分極機構を説明するための断面図であり、３
は分極用電極、４は分極ベクトル、５は浮遊電荷、６は
表面電荷、７は反電界である。An embodiment of the present invention will be described below with reference to the drawings. (Embodiment) FIG. 1 is a perspective view of a thickness-shear mode resonator according to the present embodiment, in which a resonance electrode 2 is formed on both upper and lower surfaces of a piezoelectric ceramic 1. In addition, FIG.
(B), (c) is sectional drawing for demonstrating the depolarization mechanism at the time of the heat treatment of the polarized piezoelectric ceramic by a pyroelectric effect.
Is a polarization electrode, 4 is a polarization vector, 5 is a floating charge, 6 is a surface charge, and 7 is an anti-electric field.
【００１６】まず原料としてＰｂＯ，ＴｉＯ2，Ｚｒ
Ｏ2，ＳｎＯ2，Ｎｂ2Ｏ5，Ｃｒ2Ｏ3，Ｍｎ3Ｏ4を（表
１）の組成となるように正確に坪量し、ボールミルによ
りよく混合した。First, as raw materials PbO, TiO 2 , Zr
O 2 , SnO 2 , Nb 2 O 5 , Cr 2 O 3 , and Mn 3 O 4 were accurately weighed so as to have the composition shown in Table 1 and mixed well by a ball mill.
【００１７】[0017]
【表１】 [Table 1]
【００１８】なお原料はこれらのみに限られるものでな
く化学反応により（化５）に示す圧電磁器組成物を生成
するものであれば他の化合物を使用しても良い。次に前
記混合物を８５０℃の温度で仮焼し、さらにボールミル
により粉砕した。これを乾燥した後、結合剤としてのポ
リビニールアルコール水溶液を加え、造粒した後１ton/
cm2の圧力で加圧成形し、縦５０ｍｍ、横４５ｍｍ、高
さ７ｍｍの成形体を得た。ここで得られた成形体を閉炉
中で１１５０〜１２９０℃の温度で１時間焼成し、得ら
れた圧電磁器より厚みすべり振動共振子を以下のように
して作製した。The raw materials are not limited to these, and other compounds may be used as long as they produce the piezoelectric ceramic composition shown in (Chem. 5) by a chemical reaction. Next, the mixture was calcined at a temperature of 850 ° C. and further pulverized by a ball mill. After drying, an aqueous solution of polyvinyl alcohol as a binder was added, and the mixture was granulated and then 1 ton /
Pressure molding was performed at a pressure of cm 2 to obtain a molded body having a length of 50 mm, a width of 45 mm, and a height of 7 mm. The molded body obtained here was fired in a closed furnace at a temperature of 1150 to 1290 ° C. for 1 hour, and a thickness-shear vibration resonator was manufactured from the obtained piezoelectric ceramic as follows.
【００１９】まず圧電磁器矩形板を研磨して厚み５ｍｍ
の圧電磁器１とした後、両面に銀電極を焼き付けて分極
電極３を形成後、１２５〜１８５℃のシリコンオイル中
で３．０〜４．０ｋＶ／ｍｍの直流電界を３０分間印加
して分極処理し、ついで所定の条件で熱処理を行った。
次に厚み方向に０．５ｍｍ厚みに切断し、０．０５μｍ
Ｃｒ−１μｍＡｕの二層蒸着膜よりなる共振電極２を切
断面に形成し、分極方向に切断することにより図１に示
した矩形板状の厚みすべりモード共振子を得た。これら
の試料につき密度ρ、比誘電率ε11 T／ε0電気機械結合
係数ｋ15を測定した。耐熱性は共振子を２８０℃のホッ
トプレート上で１分間保持した後、３０分経過時点での
ｋ15および共振周波数の変化率を測定した。ｋ15≧０．
３、｜ｋ 15変化率｜≦５％、｜共振周波数変化率｜≦
０．３％のものを耐熱性良好と判定した。First, a piezoelectric ceramic rectangular plate is polished to a thickness of 5 mm.
After baking silver electrodes on both sides
After forming the electrode 3, in silicon oil at 125-185 ° C
To apply a DC electric field of 3.0 to 4.0 kV / mm for 30 minutes
Then, a polarization treatment was performed, and then a heat treatment was performed under predetermined conditions.
Next, cut to a thickness of 0.5 mm in the thickness direction,
Cut off the resonance electrode 2 composed of a two-layer deposited film of Cr-1 μm Au.
Formed in cross section and cut in the direction of polarization shown in FIG.
Thus, a rectangular plate-shaped thickness shear mode resonator was obtained. these
Density ρ, relative permittivity ε per sample11 T/ Ε0Electromechanical coupling
Coefficient kFifteenWas measured. The heat resistance is as follows.
After holding on the plate for 1 minute, 30 minutes later
kFifteenAnd the change rate of the resonance frequency was measured. kFifteen≧ 0.
3, | k FifteenChange rate | ≦ 5%, | resonance frequency change rate | ≦
One having a heat resistance of 0.3% was judged to have good heat resistance.
【００２０】耐湿性については上記矩形板状厚みすべり
モード共振子を温度６０℃、相対湿度９０〜９５％の雰
囲気下に２００時間さらした後の共振周波数変化率とｋ
15変化率を測定した。ｋ15≧０．３、｜ｋ15変化率｜≦
５％、｜共振周波数変化率｜≦０．２％のものを耐湿性
良好と判定した。Regarding the moisture resistance, the resonance frequency change rate and k after exposing the rectangular plate-shaped thickness-slip mode resonator to an atmosphere at a temperature of 60 ° C. and a relative humidity of 90 to 95% for 200 hours are described.
15 rates of change were measured. k 15 ≧ 0.3, | k 15 change rate | ≦
Those having 5%, | resonance frequency change rate | ≦ 0.2% were determined to have good moisture resistance.
【００２１】以上の結果を、磁器焼成温度（密度最大）
とともに（表２）、（表３）にまとめた。Based on the above results, the porcelain firing temperature (maximum density)
(Table 2) and (Table 3).
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【表３】 [Table 3]
【００２４】（表４）に示すように、試料１〜３につい
て分極条件、分極後熱処理条件を種々に変えた場合の共
振子特性を（表５）に示す。As shown in (Table 4), the resonator characteristics of Samples 1 to 3 when the polarization conditions and post-polarization heat treatment conditions were variously changed are shown in (Table 5).
【００２５】[0025]
【表４】 [Table 4]
【００２６】[0026]
【表５】 [Table 5]
【００２７】また温度サイクル（外１）前後での共振周
波数の変動（（ｆr−ｆr0）／ｆr0の値；％）も上記共
振子により測定し（表３）、（表５）に示した。Further temperature cycles (out 1) variations in the resonant frequency before and after ((value of f r -f r0) / f r0 ;%) was also measured by the resonator (Table 3), in (Table 5) Indicated.
【００２８】[0028]
【外１】 [Outside 1]
【００２９】温度サイクルによる共振周波数変動につい
ては０．３％以下のものを良品と判定した。With respect to the variation of the resonance frequency due to the temperature cycle, those having a resonance frequency of 0.3% or less were judged to be good.
【００３０】以下本実施の形態について表を参照しなが
ら説明する。（表１）〜（表５）によるとα＜０．０２
の試料４は耐湿試験後の共振周波数変化が大きく（０．
２％以上）、α＞０．０８の試料７はキュリー温度が３
００℃以下に低下し、耐熱試験で脱分極したことから本
発明の範囲から除外した。Hereinafter, the present embodiment will be described with reference to a table. According to Tables 1 to 5, α <0.02
Sample 4 has a large change in resonance frequency after the moisture resistance test (0.
Sample 7 with α> 0.08 has a Curie temperature of 3
Since the temperature dropped to 00 ° C. or less and depolarized in the heat resistance test, it was excluded from the scope of the present invention.
【００３１】またβ＜０．００２である試料８，９は温
度サイクルによる共振周波数変化が大きく（０．３％以
上）、β＞０．０５の試料１２は圧電性が低下（ｋ15＜
０．３）するため本発明の範囲から除外した。Samples 8 and 9 with β <0.002 show a large change in the resonance frequency due to the temperature cycle (0.3% or more), and Sample 12 with β> 0.05 has a low piezoelectricity (k 15 <
0.3) was excluded from the scope of the present invention.
【００３２】さらにＡ＜０．０２である試料１３は耐熱
性が低下（｜共振周波数変化率｜＞０．３％）してお
り、Ａ＞０．０５である試料１６はキュリー温度が３０
０℃以下に低下し、耐熱試験で脱分極したことから本発
明の範囲から除外した。Sample 13 with A <0.02 has reduced heat resistance (| resonance frequency change rate |> 0.3%), and sample 16 with A> 0.05 has a Curie temperature of 30.
Since the temperature dropped to 0 ° C. or less and depolarized in the heat resistance test, it was excluded from the scope of the present invention.
【００３３】さらにまた、Ｂ＜０．４６である試料１７
は温度サイクルによる共振周波数変化率が大きく（０．
３％以上）、Ｂ＞０．７８である試料２０は圧電性が低
下している（ｋ15＜０．３）ため本発明の範囲から除外
した。Furthermore, Sample 17 with B <0.46
Has a large change rate of the resonance frequency due to the temperature cycle (0.
Sample 20 with B> 0.78 was excluded from the scope of the present invention because the piezoelectricity was reduced (k 15 <0.3).
【００３４】またＣ＜０．２５である試料２１は焼結性
および圧電性が低下している（ｋ15＜０．３）ため、Ｃ
＞０．４５である試料２４は耐熱後の共振周波数変化率
が０．３％を超え、温度サイクルによる共振周波数変化
率が０．３％以上と大きくなっているため本発明の範囲
から除外した。Sample 21 with C <0.25 has reduced sinterability and piezoelectricity (k 15 <0.3).
The sample 24 having a ratio of> 0.45 had a rate of change in resonance frequency after heat resistance of more than 0.3% and a rate of change in resonance frequency due to temperature cycling as large as 0.3% or more, and thus was excluded from the scope of the present invention. .
【００３５】副成分であるＣｒ2Ｏ3およびＭｎ3Ｏ4（少
なくとも１種）の添加量については、主成分１００重量
％に対して０．０５重量％未満の試料２５、２６、３
１、３５では温度サイクルによる共振周波数変化率が
０．３％以上と大きいため、また０．８重量％を超える
試料２９、３４、３８では焼結体密度が７．５ｇ／cm3
以下に低下するとともに圧電性が低下している（ｋ15＜
０．３）ため本発明の範囲から除外した。Regarding the addition amount of Cr 2 O 3 and Mn 3 O 4 (at least one type) as the sub-components, samples 25, 26, and 3 were less than 0.05% by weight based on 100% by weight of the main component.
In Examples 1 and 35, the change rate of the resonance frequency due to the temperature cycle was as large as 0.3% or more, and in Samples 29, 34 and 38 exceeding 0.8% by weight, the sintered body density was 7.5 g / cm 3.
And the piezoelectricity decreases (k 15 <
0.3), and thus excluded from the scope of the present invention.
【００３６】分極条件については（表４）、（表５）に
示したように分極温度１３０℃未満（加工条件ア）では
分極未飽和で、分極温度１８０℃を超える温度（加工条
件エ）では圧電磁器１の抵抗が低下し、３．０ｋＶ／ｍ
ｍ以上の電圧が印加できなくなる。また、分極時の直流
印加電圧については本発明の分極温度範囲であっても
３．０ｋＶ／ｍｍ以下（加工条件オ）では分極未飽和と
なるため本発明の範囲から除外した。As shown in (Table 4) and (Table 5), the polarization condition is that the polarization is not saturated when the polarization temperature is lower than 130 ° C. (processing condition a), and the polarization is higher than 180 ° C. (processing condition d). The resistance of the piezoelectric ceramic 1 is reduced to 3.0 kV / m
m or more cannot be applied. Also, the DC applied voltage during polarization was excluded from the scope of the present invention because the polarization was not saturated at 3.0 kV / mm or less (processing condition E) even in the polarization temperature range of the present invention.
【００３７】また分極後の熱処理条件についても（表
４）、（表５）で示したように分極用電極３間の短絡な
しに熱処理した試料（加工条件キ）では脱分極が顕著で
ｋ15＜０．３であった。これは、本発明の圧電磁器１は
焦電効果が比較的大きく、図２（ａ）に示したように分
極後は分極用電極３の表面電荷６と浮遊電荷５とが釣り
合っている状態にあるが、分極用電極３間の短絡なしに
圧電磁器１を１５０℃以上の温度で長時間熱処理した場
合には、図２（ｂ）に示すように分極ベクトル４とは反
対方向の分極を打ち消すような反電界７が生じるため、
図２（ｃ）に示すように分極が減少するからである。熱
処理温度については１５０℃以下（加工条件ク）では半
田耐熱後の共振周波数変化率が０．３％以上と大きく、
２５０℃以上（加工条件サ）では熱処理温度×熱処理時
間の積が１８００（℃・時間）以上となるような時間熱
処理すると脱分極が大きく（ｋ15＜０．３）なるため本
発明の範囲から除外した。１５０〜２５０℃の温度範囲
であっても熱処理温度と熱処理時間の積が１８００（℃
・Ｈｒ）以下（加工条件ス）であれば耐熱後の共振周波
数変化もしくはｋ15変化が大きいため本発明の範囲から
除外した。As to the heat treatment conditions after polarization (Table 4) and Table 5 (Table 5), the samples heat-treated without short-circuiting between the polarization electrodes 3 (working condition key) showed remarkable depolarization and k 15 <0.3. This is because the piezoelectric ceramic 1 of the present invention has a relatively large pyroelectric effect, and the surface charge 6 and the floating charge 5 of the polarization electrode 3 are balanced after polarization as shown in FIG. However, when the piezoelectric ceramic 1 is heat-treated at a temperature of 150 ° C. or more for a long time without short-circuiting between the polarization electrodes 3, the polarization in the direction opposite to the polarization vector 4 is canceled as shown in FIG. Since such an anti-electric field 7 is generated,
This is because the polarization decreases as shown in FIG. When the heat treatment temperature is 150 ° C. or less (processing condition C), the resonance frequency change rate after solder heat resistance is as large as 0.3% or more.
At 250 ° C. or higher (processing conditions), if heat treatment is performed for such a time that the product of heat treatment temperature × heat treatment time is 1800 (° C. · hour) or more, the depolarization becomes large (k 15 <0.3). Excluded. Even in the temperature range of 150 to 250 ° C., the product of the heat treatment temperature and the heat treatment time is 1800 (° C.
· Hr) or less (excluding from the scope of the present invention for the resonance frequency change or k 15 changes after the heat resistance when machining conditions scan) is large.
【００３８】[0038]
【発明の効果】以上本発明によると、厚みすべりモード
共振を利用した発振子・フィルタ用圧電磁器で比較的低
温での焼成が可能で、電気機械結合係数が比較的大き
く、２８０℃近傍の半田付け実装温度でも電気特性変化
の少ない、温度サイクルによる共振周波数変化の少ない
圧電磁器組成物を提供することができる。As described above, according to the present invention, a piezoelectric ceramic for an oscillator or a filter utilizing thickness-shear mode resonance can be fired at a relatively low temperature, has a relatively large electromechanical coupling coefficient, and has a soldering temperature of about 280 ° C. It is possible to provide a piezoelectric ceramic composition having little change in electric characteristics even at the mounting temperature and little change in resonance frequency due to a temperature cycle.
【図１】本発明の一実施の形態における厚みすべりモー
ド共振子の斜視図FIG. 1 is a perspective view of a thickness-shear mode resonator according to an embodiment of the present invention.
【図２】（ａ）本発明の一実施の形態における焦電効果
による分極済み圧電磁器熱処理時の脱分極機構を説明す
るための分極後の圧電磁器の断面図 （ｂ）同熱処理時の断面図 （ｃ）同熱処理後の断面図FIG. 2A is a cross-sectional view of a piezoelectric ceramic after polarization for explaining a depolarization mechanism during heat treatment of a polarized piezoelectric ceramic due to a pyroelectric effect in one embodiment of the present invention; Figure (c) Sectional view after heat treatment
１ 圧電磁器 ２ 共振電極 ３ 分極用電極 ４ 分極ベクトル ５ 浮遊電荷 ６ 表面電荷 ７ 反電界 Reference Signs List 1 piezoelectric ceramic 2 resonant electrode 3 electrode for polarization 4 polarization vector 5 floating charge 6 surface charge 7 demagnetizing field
Claims (2)
成分としてＣｒ2Ｏ3およびＭｎ3Ｏ4の少なくとも一種を
前記主成分１００重量％に対し、０．０５〜０．８重量
％添加して形成した圧電磁器組成物。 【化１】 1. A main component represented by the general formula (Chemical Formula 1), and at least one of Cr 2 O 3 and Mn 3 O 4 as a subcomponent is 0.05 to 0. A piezoelectric ceramic composition formed by adding 8% by weight. Embedded image
成分としてＣｒ2Ｏ3およびＭｎ3Ｏ4の少なくとも一種を
前記主成分１００重量％に対して、０．０５〜０．８重
量％添加、混合する第１の工程と、次にこの混合物を成
形して焼成し、焼結体を得る第２の工程と、次いでこの
焼結体表面に分極用電極を形成し、１３０〜１８０℃の
温度範囲において３．０ｋＶ／ｍｍ以上の直流電界を印
加して分極する第３の工程と、その後この分極済み焼結
体の分極用電極間を短絡して、１５０〜２５０℃の温度
下で熱処理温度（℃）と熱処理時間（時間）の積が１８
００以上となる条件下で熱処理する第４の工程とを備え
たことを特徴とする圧電磁器組成物の製造方法。 【化２】 2. A main component represented by the general formula (Chemical Formula 2) and at least one of Cr 2 O 3 and Mn 3 O 4 as subcomponents in an amount of 0.05 to 0 with respect to 100% by weight of the main component. A first step of adding and mixing 0.8% by weight, a second step of forming and firing this mixture to obtain a sintered body, and then forming a polarizing electrode on the surface of the sintered body; A third step of applying a DC electric field of 3.0 kV / mm or more in a temperature range of 130 to 180 ° C. to polarize, and then short-circuiting between the polarizing electrodes of the polarized sintered body to obtain 150 to 250 ° C. The product of the heat treatment temperature (° C.) and the heat treatment time (hour) is 18
And a fourth step of performing a heat treatment under a condition of at least 00. Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10136386A JPH11322419A (en) | 1998-05-19 | 1998-05-19 | Piezoelectric porcelain composition and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10136386A JPH11322419A (en) | 1998-05-19 | 1998-05-19 | Piezoelectric porcelain composition and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11322419A true JPH11322419A (en) | 1999-11-24 |
Family
ID=15173950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10136386A Pending JPH11322419A (en) | 1998-05-19 | 1998-05-19 | Piezoelectric porcelain composition and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11322419A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1354861A1 (en) * | 2000-12-28 | 2003-10-22 | Bosch Automotive Systems Corporation | Ceramic material and piezoelectric element using the same |
| KR100641338B1 (en) * | 2001-12-22 | 2006-10-31 | 재단법인 포항산업과학연구원 | Piezoelectric ceramic composition for accelerometer |
| US7608215B2 (en) | 2003-09-24 | 2009-10-27 | Tdk Corporation | Method of manufacturing a piezoelectric ceramic composition |
-
1998
- 1998-05-19 JP JP10136386A patent/JPH11322419A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1354861A1 (en) * | 2000-12-28 | 2003-10-22 | Bosch Automotive Systems Corporation | Ceramic material and piezoelectric element using the same |
| EP1354861A4 (en) * | 2000-12-28 | 2007-02-28 | Bosch Automotive Systems Corp | Ceramic material and piezoelectric element using the same |
| KR100641338B1 (en) * | 2001-12-22 | 2006-10-31 | 재단법인 포항산업과학연구원 | Piezoelectric ceramic composition for accelerometer |
| US7608215B2 (en) | 2003-09-24 | 2009-10-27 | Tdk Corporation | Method of manufacturing a piezoelectric ceramic composition |
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